Stabilized diazo biguanibe



Patented Oct. 20, 1942 STABILIZED DIAZO BIGUANID'E COMPOUNDS Paul P. McClellan, Old Greenwich, and Walter P. Ericks, Cos (Job, Conn., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Original application December 12,

1940, Serial No. 369,806.'- Divided and this application August 30, 1941, Serial No. 409,061

4 Claims.

This invention relates to a new class of chemical compounds, to intermediates and dyes obtained therefrom, and to their methods of preparation.

The principal object of this invention is to prepare new stabilized diazo compounds, preferably those soluble in water and in the more commonly used organic solvents. I

Among the stabilized diazo compounds included herein are, more especially, the reaction products. of an ice color diazo component with an alkylol or an alkoxyalkylol derivative of biguanide. Inasmuch as these derivatives each exist in several tautomeric forms, the reaction products prepared from any one may occur as a mixture of isomers which readily undergo rearrangement. Hence, assignment of a definite chemical formula is problematical.

However, the chemical properties of the prodnets and the particular method or methods of preparation disclosed herein cause one of the isomers to appear in excess, and under the present conditions the monomeric form is produced predominantly. Thus the alkylol and alkoxyalkylol in which R represents the nucleus of an aromatic amine such as the nucleus of an ice color diazo component; and R2 is an alkylol or alkoxyalkylol group.

These stabilized diazo compounds are resistant to percussion and even when heated in a direct flame decompose without the hazard of an explosion. When in a dry condition or in an alkaline solution they are stable at temperatures encountered throughout all seasons of the year, and hence may be stored indefinitely. However, these reaction products possess the property of splitting into their original components by treatment with acids at elevated temperatures or with steam containing volatile acid vapors. If this splitting occurs in the presence of an icecolor coupling component the regenerated active diazotized component becomes available immediately for reaction with the coupling component and produces the corresponding azo pigment or dye.

To this end it is a further object of this invention to prepare new azo pigments and dyes by mixing an ice color coupling component and the reaction product of an ice color diazo component with an alkylol or alkoxyalkylol derivative of biguanide. As such, the mixture may or may not be colored. However, if a textile material is printed or impregnated with this mixture and then heated in the presence of an acid, the acid hydrolyzes the stable diazo compound, splitting it into its components; and the regenerated diazotized component liberated couples with the ice color coupling componentv to form an azo pigment or dye.

This acid treatment or ageing as-it is called, is preferably effected with a weak acid and at an elevated temperature. Usually formic or acetic acids are used, but various other acids as well as substances liberating acids upon being steamed such as ammonium sulfate, esters of tartaric, succinic, etc., acids may be used particularly when the printed material is subjected to a subsequent steam treatment to efiect ageing or develop the color.

Stable alkaline printing pastes can be prepared from the mixture of the ice color coupling component and the reaction product of the ice color diazo component with one of the alkylol or alkoxyalkylol derivatives by dissolving the mixture in a-solvent such as water, alcohol, acetone, etc., together with various other ingredients such as alkalies, organic bases, impregnating agents, thickeners such as starch, gum, etc., Well known to those skilled in the art. Cotton goods can be printed with this paste with the aid of a copper roll. The print is then dried and subsequently the desired color is developed by steaming in the presence of acetic acid or other volatile acid vapors. ment is produced in and on the cotton fibers in the form of the printed pattern. Such prints are bright and possess remarkable fastness to light and washing.

The facility with which the compounds and dyes'included in this invention can b used is based upon the ease with which the stabilized diazamino group present can be split and con. verted into an active diazo group by heating in the presence of an acid or an acid liberating substance. This conversion or ageing is usually effected in a steam chamber and in the presence of a coupling component. Under these conditions the active diazo group is free for such a short time interval that it does not decompose and instead couples with the coupling component (e. g. naphthol in one of the examples given below) to develop or form the color.

The following examples describe the preparation of several stabilized diazo compounds included in this invention and further give details In this manner in an insoluble azopigas to their use in dyeing and printing textile materials.

EXAMPLE 1 Ethylol biguanide reacted with. p-toluidine diazom'um hydrochloride An aqueous solution of biguanide was prepared by reacting 13.25 g. of biguanide' sulfate, 8.3 g.

of sodium hydroxide and 26.3 g. of sodium carbonate in 100 cc. of water. The solution was cooled with 150 g. of ice and 7.7 g. of p-toluidine diazonium chloride was addedito the biguanidesolution with constant stirring.v A bright yellow precipitate was formed, filtered off and the filter cake dried at room temperature to yield a brown powder. This stabilized diazo compound was slurried in an alkaline aqueous solution, cooled to 5-10 C. with ice and then reacted with 2.7 g. of ethylene oxide introduced slowly and with constant stirring until all of the stabilized diazo compound was in solution.

This solubilized diazo compound has the following probable formula: r

NE NH EXAM-PH: 11

When the stabilized diazo compound of Example I was reacted with glycidol in an aqueous solution' to which some sodium hydroxide had'been added, a stabilized diazo compound was obtained having .the'following probable formula: HaCC N;N-.I I,C-NH0 I-.CH2CH-CH2OH j IHIH IHIH (')H It was soluble in water forming a stable solution. However when mixed with a coupling component free of solubilizing groups (such as an alkaline alcohol water solution of sodium-@- naphtholate), -acidified. and heated, a water in-'. soluble organic pigment is formed.

Similarly various other members of the alkylol and alkoxyalkylol serie of derivatives of biguanide may be obtained by using as a starting material the corresponding compound containing a reactive ethylene oxide ring and a corresponding substituent in the ethylene oxide ring. Thus instead of ethylene'oxide, one or more mol. of lycidol, propylene oxide, isopropylene oxide, butylene oxide, isobutylene oxide, etc., etc., can be used in order to render the stabilized diazo compound water soluble. A number of such compounds are described in the copending applications Serial Numbers 289,398 and 289,400 of Walter P. Ericks.

It' is to be particularly noted that althoughfor ease ofdescription, the aromatic amine chosen in of the invention was p-toluidine, variou other prepared from practically any ice color diazo component. Thus other typical amines which can be diazotized and reacted with the stabilizing components include in addition to p-toluidine, among numerous othersfamili'ar tothose versed in the art, aniline as well as homologues of aniline, namely 2,4-dimethylaniline. Where still other color variations are desired, the halogen derivatives ofv aniline may be used, such as the monochloroanilines, dichloranilines; anilines substituted by hydrocarbon radicals, such as alkyl, all'zoxyradicals, for example methyl, ethyl, etc.,

methoxy,"ethoxy, etc; or anilines substituted by 'nitro radicals, jacyl derivatives thereof, and the like Similarly, although l-naphthol is given as the .most frequently; used coupling component for the dye mixture incorporating the specific stabilized cation, Serial Number 369,806, filed December 12, p

It-is to be understood that the examples herein given are merely illustrative and not limitative embodiments of this. invention .which is to. be construed broadly'andlimited solely as defined by the scope of the appended claims; 1

1 We claim:

1. A stabilized ,diazo eral formula:

compound having the 'gen- 1? {I .I R-N=N=N-'o-1 IH 'o-1 I--"1n v V YNHYVNHVYY. in which R is the nucleus of an ice color diazo component, of the benzene series and R2 is selected from thetgrou'p consisting of. an alkylol and an alkoxyalkylol group.

2. A stabilized diazo compound having the formula:

i i R.N=NN-CNH(|'|JN-XOH "NH"'NH Y in which R is the nucleus of an ice color diaz'o component of the benzene series and X is asaturated aliphatic radical having at least two carbon atoms. I I

3. 'A'stabilized diazo compound having the formula:

, 7 NH v NH in which R is the nucleus of an ice color diazo componentof the benzene series. r Y

4. Astabilized diazo' compound having the formulaz". 1

.a-N N-rpo nn c-N imononion NH NH OH in which R is the nucleus of an ice color diazo' component of the benzene series.

stable diazo compounds embraced herein can be PAUL P. McCLELLAN. WALTER. P. ERIcKs. 

